The present invention relates to a phosphine compound which is useful as a component of a catalyst system which may be used in the carbonylation of olefins, and in particular to a method of manufacturing such phosphine compounds.
WO 96/19434 discloses a process for the carbonylation of ethylene and a catalyst system for use therein. The catalyst system described in that document comprises a bidentate phosphine of general formula (R3xe2x80x94C)2Pxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94Pxe2x80x94(Cxe2x80x94R3)2, in which each R is independently a pendant, optionally substituted, organic group through which the group is linked to tertiary carbon atom C; L1, L2 are independently a linking group selected from an optionally substituted lower alkylene chain connecting the respective phosphorus atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorus atoms are linked on available adjacent carbon atoms. One example of such a bidentate phosphine is bis(di-tbutyl phosphino)-o-xylene (also known as 1,2,bis(di-t-butylphosphinomethyl)benzene).
Such catalysts may be made by mixing the phosphine ligand with a suitable source of palladium such as palladium acetate. WO 96/19434 describes the preparation of one form of the ligand via the phosphonium salt produced from the reaction of the appropriate secondary phosphine with the corresponding aromatic dihalide. In the preferred form of the phosphine ligand in WO 96/19434, R is a lower alkyl group, in particular methyl. A problem with manufacturing this ligand by the route described is that the secondary phosphine which is used (e.g. di-tbutyl phosphine) is toxic, highly reactive, smelly and flammable. We have also found that the reaction is low yielding and converts some of the di-tbutyl phosphine to a non-reclaimable waste product which must be disposed of.
Al-Salem et al in Journal of the Chemical Society (Dalton) 1979 page 1980 describes making 1,5 bis(di-t-butylphosphino)pentane by reacting lithium metal with 1,5-dibromopentane and then phosphorylating the resulting lithiated intermediate with t-butylchlorophosphine. This method, for forming a phosphine of an alkyl compound, starts from the halogenated alkyl compound. Alkyl halides typically require considerable care during storage and use and may be very unpleasant to use. Therefore using this method of making the phosphine using the non-halogenated alkyl compound as a starting material would require an extra step of converting first to the alkyl halide.
We have now found that phosphine ligands of the type described in WO 96/19434 may be prepared by a high yielding route using more benign materials which produce less waste phosphorus product than the route described in WO 96/19434.
According to the invention, a method of manufacturing a compound of general formula (R3xe2x80x94C)2Pxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94Pxe2x80x94(Cxe2x80x94R3)2 in which each R is independently a pendant, optionally substituted, organic group through which the group is linked to tertiary carbon atom C; L1, L2 are independently a linking group selected from an optionally substituted lower alkylene chain connecting the respective phosphorus atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorus atoms are linked on available adjacent carbon atoms comprises the steps of
i) reacting together a compound of formula Hxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94H with an organometallic compound to form an intermediate compound of formula Mxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94M, where M is an alkali metal atom,
ii) reacting said intermediate compound with a compound of formula (R3xe2x80x94C)2Pxe2x80x94A, where A is a halogen atom, to form said compound of general formula (R3xe2x80x94C)2Pxe2x80x94L1xe2x80x94Xxe2x80x94L2Pxe2x80x94(Cxe2x80x94R3)2.
The compound of general formula (R3xe2x80x94C)2Pxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94Pxe2x80x94(Cxe2x80x94R3)2 may be useful as a component of a catalyst compound. In particular WO 96/19434 describes the use of such compounds as bidentate ligands which, when used together with a Group VIII metal such as palladium are effective catalysts for the carbonylation of olefins.
The pendant, optionally substituted organic groups, R may be independently selected from a wide range of components. Preferably, the pendant groups are optionally substituted lower alkyl, e.g. C1-8, and may be branched or linear.
Particularly preferred is when the organic groups, R, when associated with their respective carbon atom, form composite groups which are at least as sterically hindering as tert-butyl. Steric hindrance in this context is as discussed at page 14 et seq of xe2x80x9cHomogeneous Transition Metal Catalysisxe2x80x94A Gentle Artxe2x80x9d, by C Masters, published by Chapman and Hall, 1981. In one preferred embodiment, the organic groups R are all methyl groups, i.e. a preferred form of R3xe2x80x94C group is a tertiary butyl group.
The linking groups, L1and L2, are independently selected from an optionally substituted, particularly lower alkylene, e.g. C1 to C4, substituted, lower alkylene, e.g. C1 to C4 chain. Especially preferred is when both L1 and L2 are methylene.
The bridging group X is, preferably, an aryl moiety, e.g. a phenyl group, which may be optionally substituted, provided that the two phosphorus atoms are linked to adjacent carbon atoms, e.g. at the 1 and 2 positions on the phenyl group. Optional substitution of the aryl moiety may be by other organic groups, e.g. alkyl, particularly C1-8, aryl, alkoxy, carbalkoxy, halo, nitro, trihalomethyl and cyano. Furthermore, the aryl moiety may be a fused polycyclic group, e.g. naphthalene, biphenylene or indene.
Examples of compounds which may advantageously be made by the method according to the invention are bis(di-tert-butyl phosphino)-o-xylene (also known as 1,2 bis(di-tert-butylphosphinomethyl)benzene), bis(di-t-neopentyl phosphino)-o-xylene and bis 1,2 (di-tert-butyl phosphino)naphthalene.
The reaction of a compound of formal Hxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94H with a basic organometallic compound of formula RmM to form an intermediate compound of formula Mxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94M, where M is an alkali metal atom, may be carried out by various means which are known in the art of organometallic chemistry. For example, such metallation methods are described by Wilkinson et al. in xe2x80x9cComprehensive Organometallic Chemistryxe2x80x9d at page 54; and by Lambert et al. in xe2x80x9cPreparative Polar Organometallic Chemistryxe2x80x9d.
The organometallic compound may comprise a compound of formula Rmxe2x80x94M, where Rm is an organic group which tends to withdrawn electrons from the metal atom M. Suitable organic groups include aromatic or aliphatic groups, especially alkyl groups, which may be substituted. Lower alkyl groups have been found to be particularly suitable, for example preferred Rm compounds include n-butyl, t-butyl, sec-butyl, methyl or pentyl. M may be any suitable alkali metal which forms a polar organometallic group with Rm. Suitable metals include those of Group IA, e.g. sodium, potassium or lithium. When M comprises K or NA the Rmxe2x80x94M metallating agent is preferably generated in situ by an exchange mechanism, e.g. by the reaction between Rmxe2x80x94Li and potassium or sodium t-butoxide as described by Lochman et al. in Tetrahedron Letter No. 2 pages 257-262 (1966). Preferred metallating compounds are butyl lithium, butyl sodium and butyl potassium, the latter compounds preferably being formed in situ by the reaction of butyl lithium with potassium or sodium t-butoixde.
Alternative organometallic compounds are also known in the art and may comprise Me3SiCH2K, alkali amides MNH2 preferably used in liquid ammonia, lithium dialkylamides e.g. lithium diisopropylamide (LDA), lithium, sodium or potassium metals, metal hydrides e.g. KH in the presence of coordinating compounds.
The reaction between RmM and Hxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94H may be carried out in the presence of a solvent. Any solvent used must not contain any component which reacts with the intermediate compound, and suitable such solvents will be well known to the skilled chemist. Favoured solvents include dry alkyl ethers e.g. diethyl ether, methyl t-butyl ether, di(n-propyl)ether; tetrahydrofuran(THF), and hydrocarbons such as hexane and heptane.
The reaction between RmM and Hxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94H may be beneficially carried out in the presence of a basic compound which is capable of forming a complex with the metal. A preferred complexing agent is tetramethylethylenediamine(TMEDA). The presence of TMEDA is greatly preferred when the metallating agent is alkyl lithium or alkyl sodium. When alkyl potassium (or alkyl lithium/potassium t-butoxide mixture) is used, we have found that the reaction proceeds satisfactorily in the absence of TMEDA.
The mole ratios of metallating agent:Hxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94H are preferably in the range 1:1 to 10:1, more preferably at least 1.5:1. The preferred ratio depends upon the nature of the metallating agent used, for example when alkyl lithium is used a ratio of Rxe2x80x94Li:Hxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94H of 3:1 may be preferred. Higher ratios may be preferred to encourage the formation of di-substituted product rather than mono-substituted compounds.
A preferred ratio of RmM:complexing agent is in the range 1:1-4:1, especially preferred is a ratio of about 1:1 to about 2:1.
It is preferred to conduct the metallation reaction between RmM and Hxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94H at a temperature in the range xe2x88x9220 to 150xc2x0 C., more preferably at room temperature or above. The optimum temperature and reaction time depends upon the identity of the reactants, in particular upon the alkali metal which is used. For example we have found, using o-xylene as the compound to be metallated that when alkyl lithium is used, the reaction proceeds well at room temperature (i.e. about 20-22xc2x0 C.) whereas reactions using alkyl
sodium and potassium are preferably conducted at about 60, (e.g. 50-70xc2x0 C.) and about 80xc2x0 C. (e.g. 70-90xc2x0 C.) respectively. The intermediate compound, Mxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94M may be isolated from the reaction mixture prior to conducting the reaction between Mxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94M and the compound of formula (R3xe2x80x94C)2Pxe2x80x94A. However isolation of the intermediate may not be necessary and the reaction has been found to proceed very satisfactorily when the intermediate is not isolated. When the intermediate product Mxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94M can be separated relatively easily, for example if it is in a different physical form from the starting materials, then it may be advantageous to isolate the intermediate form the reaction mixture to encourage the formation of more intermediate. We have found that the reaction mixture may contain partially reacted compounds of formula Mxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94H which may be reacted to completion by the addition of further quantities of RmM and complexing agent if used.
The phosphorylation reaction between the intermediate product Mxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94M and the halophosphine (R3xe2x80x94C)2Pxe2x80x94A is also carried out in the presence of a solvent and similar solvents to those used for the metallation are suitable, e.g. ethers, C5+ alkanes and petroleum ethers. We have found that, when the metal used is potassium, the reaction is favoured when diethyl ether is used as a solvent for the phosphorylation reaction, although an alkane e.g. heptane, may be preferred for the metallation reaction. Also, even when sodium or lithium is used as the metal species, it may be beneficial to use a different solvent for the phosphorylation from that used for the metallation, e.g. to enable higher temperatures to be used in one reaction yet allow an easy separation of the solvent from the product of the second reaction.
The phosphorylation reaction may be conducted at elevated temperatures, e.g. at temperatures of 60xc2x0 C. or greater, but it is preferred to conduct the reaction at room temperature or below, e.g. at xe2x88x9220 to 25xc2x0 C.
The compound of general formula (R3xe2x80x94C)2Pxe2x80x94L1xe2x80x94Xxe2x80x94L2xe2x80x94Pxe2x80x94(Cxe2x80x94R3)2 may be isolated from the reaction mixture by distilling off the excess solvent, preferably under vacuum and then extracting the product compound into a solvent, e.g. methanol, from which it may be precipitated.
The invention will be further described, by way of example only, below. In all reactions, the reactants and apparatus used were prepared to allow the reaction to proceed in anhydrous and anaerobic reaction conditions.